Method of making siloxanes



. 2,485,928 mrrnon or MAKING smoxmns Philip 0. Servais, Midland,1tfloh.,assignorto The Dow Chemical Company, Midland; Mlch., a corporation oi Delaware No Drawing. Application mm- 8, 1947.

Serial No. 778,742

6 Claims. (CI. 280-4482) The present invention is directed to the pro duction of siloxanes from silanes.

The conventional method for the preparation of siloxanes involves the hydrolysis of silanes which contain hydrolyzable atoms or radicals, followed by the condensation of the hydrolyzate. This process has been used for many years, both in the work of Kipplng and in the recent commercial production of siloxanes. When this method is employed in conjunction with hydrocarbonyl silicon chlorides, the by-product is hydrogen chloride, generally in dilute form. When hydrocarbonyl alkoxy silanes are employed the byproduct is dilute alcohol. In each of these instances the value of the atom or radical which is removed by hydrolysis is lost as far as commercial utilization is concerned.

It is an object of this invention to provide methods for the conversion of silanes to siloxanes with the recovery of by-products in a commercially useful form.

Other objects and advantages will be apparent from the following description.

In accordance with the present invention a silane or a mixture of silanes is condensed. The silane or mixture of silanes has on the average from one to two monovalent alkyl or aryl radicals linked to the silicon. The remaining valences of the silicon atoms of the silane are satisfied by chlorine atoms and alkoxy radicals. Condensation is efiected in liquid phase with FeCla in admixture with the silane. In order to effect the condensation single silicon atoms have both chlorine and alkoxy linked thereto. and the total number of alkoxy radicals is at least as great as the number of chlorine atoms.

I Silanes which are condensed in accordance with this invention are characterized by the general formulae RSHCR'MCI and RaSiOR'Cl, in which R represents an alkyl or aryl radical and R represents an alkyl group. These alkoxy and -chl0ro substituted silanes, particularly (CH3) QSiOCgHtCl may be formed as by-products in the commercial manufacture of orsano silicon compositions by the Grignard process in ether solution. Alternatively, they may be prepared by reacting a silane ester having the general formula R4 mSi(OR.')m, wherein R represents a monovalent alkyl or aryl radical, R represents an alkyl group and m is an integer equal to 1, 2, 3, or 4, with a polychloro silane having the general formula RA-nSiCln, wherein It represents an alkyl or aryl radical and n is an integer equal to 2 or 8.

As a result of this reaction, one or more or thechlorine atoms on the polychloro silane is interchangedwith a corresponding number or alkoxy radicals of the silane ester to form compounds having both chlorine and alkoxy substituents on the same silicon atom. Presence of a minor proportion of free acid aids in promoting the interchange reaction. It is to be noted that in some instances the entire product or products of the interchange reaction are compounds having the requisite number and ratio of alkoxy and chlorine substituents for condensation in accordance with the invention. Thus; when a diorgano dichloro silane is reacted with an equivalent amount of a diorgano dialkoxy silane, all the silanes produced may be condensed in accordance herewith.

An alcohol may be employed in lieu of the silane ester to provide alkoxy radicals for interchange with the chlorine atoms of the chloro silane. In this instance HCl, which is formed as a by-prodnot, is preferably removed prior to the condensation step. In interchange reactions of the foregoing types, the R groups are inert.

Inthe condensation of silanes to siloxanes in accordance with the present invention, a'chlorine atom combines with the hydrocarbon portion of an all-roxy radical to form an alkyl chloride. Because of the relatively low boiling points of the alkyl chlorides, they are readily separated in substantially pure form from the siloxane residue. If a silane ester and a polychloro silane are mixed in the presence of F6013, condensation occurs during or upon completion of the interchange.

The rate of reaction is dependent to some extent upon the proportion of FeCla in the mixture. I prefer to employ at least 0.03% by weight of FeCl: to bring about condensation at a commercially satisfactory rate. By increasing the amount of FeCla, condensation can be accom plished more rapidly, resulting in an increase in the viscosity of the siloxane product. As large a quantity of catalyst may be employed as desired, although it is generally preferable to employ less than 3% by weight, as the use of larger amounts may cause the reaction to proceed at a faster rate than can be managed with facility. The amount of catalyst employed is relatively independent of the particular compound or mixture of compounds involved. Presence of a small amount of HCl will serve to promote catalysis. FeClz appears to be the only suitable catalyst for the condensation, as other metallic chlorides do not give the desired results.

The present condensation is effected at a temperature above 50 C. and below the temperature 3 at which destructive distillation of the siloxane would occur. The reaction is generally complete at tem eratures below 200 0., which temperatures are preferred.

When an alkoxy silane or an alcohol and a chloro silane are admixed prior to condensation, there is generally sufflcient heat generated by the interchange reaction between the alkoxy radical and the chlorine atom to bring about condensation at the desired rate if FeCla is present. However, in other instances, particularly when an alkoxy chloro silane is the starting material, the silane is heated to the temperature range indicated. Control of the condensation reac ion is readily accomplished by allowing the heat of reaction to cause boiling and by refluxing the materials so boiled. This provides for the removal of the heat of reaction. Asis known, the specific temperature to which the refluxing reaction mixture is held may be controlled by adjusting the pressure on the reaction mixture. With adequate indirect temperature control, the reaction mixture may be maintained at any desired temperature below that at which refluxing occurs.

The properties of the siloxane products are influenced considerably by the amount of catalyst present, the temperature at which the reaction is carried out and the length of time the mixture is heated. A relatively low temperature and small proportion of catalyst generally results in the formation of low viscosity siloxane liquids. By increasing the proportion of catalyst and/or employing higher temperatures, with consequent increase in the rate of reaction, higher viscosity liquids are obtained.

I have found that the presence of a suitable organic solvent, such as toluene, inhibits rapid reaction. For this reason. it may be advantageous to dilute the alkoxy chloro silane with solvent when low viscosity siloxanes are desired as the product. The proportion of solvent to' silane is not critical, although I have found that equal parts by volume of solvent and silane effects this result. Preferably the solvent is present in the mixture before the catalyst is added.

Separation of by-product alkyl chloride may be accomplished through distillation as the condensation proceeds. When evolution thereof ceases the reaction is complete.

An outstanding feature of this invention lies in the formation of substantially pure alkyl chloride as a by-product, which is of commercial importance because it can be recycled for reaction directly with silicon or it may be reacted with SiCl4 by the Grignard method. If desired, it can be stored either as gas or liquid for future use. This is in contrast with the present commercial practice wherein by-products are discarded.

The siloxane condensation products obtained by practicing this invention range from low viscosity, water white liquids to high viscosity fluids having substantially no flow at room temperature. They are characterized by both linear and cyclic structures, which contain alternate silicon and oxygen atoms and there are generally one or two hydrocarbonyl groups attached to the silicon atom. Any excess alkoxy radicals not removed in the condensation are present in the siloxane produced and are linked to silicon atoms therein. These alkoxy radicals may be hydrolyzed, if desired.

A better understanding of the invention may be had by reference to the following examples, which are not to be construed as limiting the scope thereof.

Example 1 Equal mol ratios of CH2Si(OC2Hs)3 and CHaSiCla were combined and 1% FeCla by weight was added to the mixture. On heating the mixture, CzHsCl evolution began at 75 C. pot temperature and a substantially theoretical yield thereof was obtained. The balance of the mixture was converted to methyl siloxane;

Example 2 One mol of CHsOH was added to one mol of (CH3)2SlC12. An exchange reaction took place, whereby there was formed (CH3)2S1OCH3C1 and HCl, the latter being removed by distillation. 1% by weight FeCla was then added to the (CH3)2S1OCH3C1 and the mixture was heated to C. pot temperature. Reaction was rapid at this temperature and a theoretical yield of CHaCl was obtained. There was obtained also liquid polymeric dimethyl siloxane, having the formula [(CHaMSiOh in substantially theoretical amount.

Example 4 A mixture of equal mol ratios of CeHsSiCla. CsHsCHaSiClz, and C'HsSiCla was treated with anhydrous C2H5OH in amount equivalent to one half the total chloride content of the silane mixture to provide ethoxy radicals for interchange with the Cl atoms. After removal of excess HCl by-product of the interchange, the residual mixture was cooled, 0.5% by weight FeCla was added and the mixture was reheated. Reaction became vigorous when the pot temperature reached C., and the temperature quickly rose to C. C2H5Cl was evolved rapidly and was collected. The balance of the mixture was a high molecular weight siloxane polymer.

Example 5 Example 4 was repeated, except that the mixture was diluted with an equal volume of toluene before addition of catalyst. Presence of toluene slowed the evolution of ethyl chloride. A liquid polymer was obtained of lower molecular weight than in Example 4 in addition to the ethyl chloride by-product.

Example 6 Equimolar ratios of (CH3) 281012 and (CHaMSKOCaHa):

were combined and 0.1% RC1: was added to the mixture. C2H5C1 evolution was slow at a pot temperature of 90 C. The mixture was then cooled and saturated with HCl to promote the interchange of chlorine and ethoxyl. Heating was then resumed and evolution of 0211501 was approximately double that previously observed.

being removed by distillation.

asons Nearly the theoretical quantity of CaHtCl was obtained. The residual product was polymeric dimethyl siloxane in liquid form.

Example 7 pcrature, evolution of CaHsCl was so rapid that the flask had to be cooled occasionally to control the rate of reaction. A theoretical yield of CzHsCl was obtained. while the yield of liquid polymeric phenyl methyl siloxane residue was 92.5% of theoretical.

Example 8 One mol of CeHsSiCl: was combined with two mols of CzHaOH. An interchange reaction occurred with the formation of CsHsSKOCzI-Is) 201 and HCl, the latter being removed by fractional distillation. 0.5 per cent by weight-FeCla was added to the C6H5S1(OC2H5)2C1, which was then heated. CzHsCl was evolved at a pot temperature of 100 C. and 77.5 per cent of theoretical CzHsCl was recovered. The residual material was a siloxane polymer in liquid form.

' Example 9 .45 mol of CH3S1(OC2H5)3 and .55 mol of CsHsCHaSiClz were combined and 0.1 per cent by weight FeCla was added. The mixture was heated and CzHsCl was evolved at 90 C. pot temperature. 92 per cent of theoretical CzHsCl was obtained as distillate. The condensation product was a low viscosity liquid siloxane copolymer.

Example 10 .50 mol of CH3S1(OC2H5)3, .25 mol of (CeH5)2SiClz and .25 mol of CsHsCHsSiClz were combined and 0.1 per cent by weight FeCh was added. The mixture was heated to 90-100 C. pot temperature. On completion of the reaction 77 per cent of theoretical ethyl chloride was obtained, the balance of the mixture being converted to the phenyl methyl siloxane copolymer.

Example 11 .05 per cent by weight FeCls was added to CcH5S1(OC2H5)2Cl and the mixture was heated. 77.5 per cent of the theoretical yield of ethyl chloride was recovered, the pot temperature being maintained below 120 C. The residual siloxane was a polymer containing phenyl and ethoxy substituents on the silicon atom.

Example 12 Isopropyl alcohol was cooled to about 10 C. and an equal mol ratio of (CH3) 2SiCl2 was added slowly thereto so that the temperature was maintained below 15 C. Following addition of the (CH3)2SiC12 the mixture was warmed to 108 C. and an interchange reaction took place with formation of (CH3)2SiOCaH-1Cl and HCl, the latter The residual (CH3)2SiOC3I-I7C1 was cooled and 0.1% FeCla by weight was added. Heating was resumed and the vapor evolved below a pot temperature of 150 C. was collected. The evolved vapor was condensed and found to be substantially pure isopropyl chloride. Nearly the theoretical quantity of [(CEhSiOln was obtained as residue in the form of a low viscosity liquid.

6 Example 18 (CH3) 281012 was added slowly to butyl alcohol until equal mol ratios of the reactants were combined, the temperature being maintained below 10 C. After completion of the addition the mixture was warmed to distill oi! the HCl which was formed. The residual (CH3) 2S1OC4H9C1 was then cooled and 0.1% by weight FeCh was added, followed by refluxing for 8 hours. A yield of approximately 55% of theoretical butyl chloride was obtained. Liquid [(CHs) BS1013 was obtained as residue.

Example 14 Equal mol ratios of stearyl methyl dichloro silane and ethyl alcohol were combined while the temperature was maintained below 10 C. The mixture was heated and HCl was driven oil. After cooling, 0.1% by weight FeCla was added and the temperature was raised to 235 0., the reflux temperature of the mixture. Conversion of the mixture to ethyl chloride and low viscosity stearyl methyl siloxane polymer was complete 'after 8 hours heating at this temperature.

Having fully claim is:

1. The method of condensin monosilanes oi. the general formula Ri-nSiXn, wherein R represents a radical of the group consisting 01' alkyl and monccyclic aryl radicals, X represents a radical of the grou consisting of chlorine atoms and alkoxy radicals, and n has a value from 2 to 3 inclusive, said silanes being condensed containing both chlorine atoms and alkoxy radicals bonded to the same silicon atoms, and the number of alkoxy radicals in the silanes being condensed being at least as great as the number of chlorine atoms, which comprises contacting said silanes in liquid phase with FeCla at a temperature above 50 C. and below the temperature at which destructive distillation of the siloxane would occur, whereby condensation thereof to a siloxane is accomplished with the formation of alkyl chloride.

2. The method of producing organosiloxanes which comprises maintaining a mixture of a chloro'silane of the general formula Rl-nSlCln where R is a radical of the group consisting of alkyl and monocyclic aryl radicals and n has a described my invention, what I value from 2 to 3 inclusive and an alkoxy silane which comprises maintaining a mixture of a chlorosilane of the general formula RzSiCla where R is a radical of the group consisting of alkyl and monocyclic aryl radicals, and an alkoxy silane of the general formula R2Sl(OR')2 where R is a radical of the group consisting of alkyl and monocyclic aryl radicals and R is an alkyl radical, in liquid phase in contact with FeCh at a temperature above 50 C. and below the temperature at which destructive distillation of the siloxane would occur, whereby a slloxane and an alkyl chloride are produced.

4. The method of producing organosiloxanes which comprises maintaining a mixture of a chlorosilane of the general f01mll1afR4nsiC1n where;. l3. represents a 7 radical of the group consistingoi' alkyl and monocyc'lic'aryl radicals and n has a value from 2 to" 3 inclusive, and an alcohol of the general formula R'OH where R represents an alkyl radical, in liquid phase in contact with FeCla at a temperature above 50 C. and below the temperature at which destructive distillation of the siloxane would occur, whereby a siloxane and an alkyl chloride are produced.

5. The method of producing siloxane from a substituted silane having the general formula RnSiOR'Cl, wherein R represents a radical of the group consisting of alkyl and monocyclic aryl radicals and R represents an alkyl radical, which comprises maintaining said silane in liquid phase in contact with FeCla at a temperature above 50 C. and below the temperature at which destructive distillation of the siloxane would occur, whereby condensation is efiected to siloxane with the formation of alkyl chloride.

6. The method of making polymeric dimethyl siloxane from (CI-IDzSlOCI-IsCl, which comprises contacting said silane in liquid phase with a =minor proportion of FeCl: at a temperature- REFERENCES crrnn The following references are of record in the file of this patent:

TENTS UNITED STATES I? Number Name I Date 2,377,689 Hyde June 5, 1945 2,389,477 Wright Nov. 20, 1945 2,405,988 Barry Aug. 20, 1946 2,421,653 Sauer June 3. 1947 OTHER REFERENCES Friedei et al., Berichte der Deut. Chem.

GeselL, vol. 3 (1868-70), pages 15-19. 

